CN107684921B - Catalyst for converting TMBQ into TMHQ and preparation method thereof - Google Patents
Catalyst for converting TMBQ into TMHQ and preparation method thereof Download PDFInfo
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- CN107684921B CN107684921B CN201710810911.4A CN201710810911A CN107684921B CN 107684921 B CN107684921 B CN 107684921B CN 201710810911 A CN201710810911 A CN 201710810911A CN 107684921 B CN107684921 B CN 107684921B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- QIXDHVDGPXBRRD-UHFFFAOYSA-N trimethyl-p-benzoquinone Natural products CC1=CC(=O)C(C)=C(C)C1=O QIXDHVDGPXBRRD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000013207 UiO-66 Substances 0.000 claims abstract description 23
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 13
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 26
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000012621 metal-organic framework Substances 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- -1 amino Chemical group 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 2
- 229910003603 H2PdCl4 Inorganic materials 0.000 abstract 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229930003427 Vitamin E Natural products 0.000 description 6
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 235000019165 vitamin E Nutrition 0.000 description 6
- 229940046009 vitamin E Drugs 0.000 description 6
- 239000011709 vitamin E Substances 0.000 description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012696 Pd precursors Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KEVYVLWNCKMXJX-ZCNNSNEGSA-N Isophytol Natural products CC(C)CCC[C@H](C)CCC[C@@H](C)CCC[C@@](C)(O)C=C KEVYVLWNCKMXJX-ZCNNSNEGSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 239000013090 hafnium-based metal-organic framework Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002091 nanocage Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A catalyst for converting TMBQ into TMHQ is prepared from amino-functionalized metal-organic skeleton material NH2-UiO-66(Hf) derived HfO2Amorphous carbon and noble metal Pd nanoparticles, wherein HfO2The weight ratio of the noble metal Pd to the amorphous carbon is 1.4-5, and the content of the noble metal Pd is 0.5-5% of the total weight of the catalyst. The preparation method comprises the following steps: adding hafnium tetrachloride and 2-amino terephthalic acid into a mixed solution of dimethylformamide and hydrochloric acid, and simultaneously dropwise adding H2PdCl4Heating and stirring the solution, reducing, washing and drying to obtain Pd @ NH2-UiO-66 (Hf); then the solid is treated for hours at high temperature in inert atmosphere to obtain the catalyst Pd/HfO2@ C. The catalyst has excellent catalytic activity, selectivity and reusability when being used for converting TMBQ into TMHQ.
Description
Technical Field
The invention relates to a heterogeneous catalyst and a preparation method thereof, in particular to a catalyst for converting 2, 3, 5-Trimethylbenzoquinone (TMBQ) into 2, 3, 5-Trimethylhydroquinone (TMHQ) and a preparation method thereof.
Background
2, 3, 5-Trimethylhydroquinone (TMHQ) is an important intermediate for synthesizing Vitamin E (VE), and can be condensed with isophytol to produce vitamin E. VE is not only applied as an additive for foods, medicines, health products, cosmetics, but also increasingly used as an industrial antioxidant, and has become a hot product of great interest in recent years. With the widespread use of VE, the TMHQ demand will also increase year by year. The domestic market TMHQ is short of supply and demand, and the improvement of the production process of the TMHQ has important economic benefits. The production method of TMHQ mainly comprises a chemical reduction method and a catalytic hydrogenation reduction method. Although the chemical reduction method is easy to implement, the industrial wastewater is much, and the product quality is not stable. The catalytic hydrogenation reduction method is used for preparing TMHQ by taking 2, 3, 5-Trimethylbenzoquinone (TMBQ) as a raw material through a catalytic hydrogenation mode, and has the characteristics of high product quality, low cost, less three wastes and the like. Therefore, the development of a hydrogenation catalyst with high activity, high selectivity and high stability to convert TMBQ into TMHQ becomes a problem to be solved urgently.
The Metal Organic Frameworks (MOFs) are novel porous crystal materials which are formed by self-assembling metal centers and bridged organic ligands and have three-dimensional net-shaped ordered pore structures, have the characteristics of ultrahigh specific surface area, variety and structural diversity, chemical functionalization and the like, and show potential application prospects in the field of heterogeneous catalysis. Noble metals (such as Pd, Pt and Ru) loaded on MOFs carriers can be generally used as high-efficiency heterogeneous catalysts for catalytic hydrogenation reactions. However, the metal nanoparticle-MOFs composite materials synthesized by the conventional method still face many challenges, such as easy agglomeration of metal nanoparticles on the surface of the carrier, difficult control of the size of the metal nanoparticles, and potential damage of the subsequent reduction process to the MOFs framework structure.
NH2the-UiO-66 (Hf) is a Hf-based MOFs material, which is formed by coordination of hafnium oxide metal clusters and an organic carboxylic acid ligand aminoterephthalic acid. NH (NH)2the-UiO-66 (Hf) has a large specific surface area and a rich nanopore cage structure. As a main material, metal nanoparticles, NH can be effectively loaded2A large number of saturated Hf metal centers in-UiO-66 (Hf) which are converted to tetragonal HfO by high temperature treatment2. The existing research shows that the tetragonal phase HfO is used as a carrier2Has potential application in heterogeneous catalytic reaction. In addition, NH due to the strong interaction of the lone pair of electrons of the N atom with the d-orbital of the metal atom2NH in the-UiO-66 (Hf) skeleton2The group can effectively chelate the metal precursor, so that the height of metal ions is limited in a pore cage of MOFs, and the problem of agglomeration in the pyrolysis process can be effectively prevented. Using N, N-dimethyl formamide as solvent to synthesize NH2Adding a proper amount of Pd precursor into mother liquor of-UiO-66 (Hf), coupling the steps of MOFs construction, Pd precursor chelation and Pd precursor mild reduction, and directly preparing Pd @ NH by adopting a one-step method under the liquid phase condition2-UiO-66(Hf), where DMF acts both as a solvent to facilitate self-assembly to form NH2-UiO-66(Hf) skeleton, which in turn acts as a reducing agent to reduce the precursor to Pd nanoparticles. After pyrolysis treatment in high-temperature inert atmosphere, NH2-ligands of UiO-66(Hf) and Hf-based metal clusters to porous carbon and HfO, respectively2Nanoparticles. At the same time due to NH2The presence of the groups, the Pd nanoclusters are highly dispersed in the N-doped porous C support. Studies have shown that N-doped C carriers can simultaneously produce a large number of topological defects. Through the synergistic effect of Pd single active site and N doped porous carbon, the heterogeneous catalyst Pd/HfO with small and controllable metal particles, high dispersity and high stability is designed and synthesized2@ C, the catalyst has potential application in heterogeneous catalytic reactions.
So far, many reports have been made on the research on the MOFs in the field of catalysis, but the research on the conversion of MOFs-coated metal nanoparticles as a template into a carbon N-doped porous composite material is relatively less, especially the metal organic framework material NH2-UiO-66(Hf) encapsulated Pd nanoparticles as sacrificial template converted into N-doped Pd/HfO2The preparation of the @ C catalyst and the research of applying the @ C catalyst to the preparation of the vitamin E intermediate by TMBQ hydrogenation have not been reported.
Disclosure of Invention
The technical problem to be solved by the invention is that the catalytic hydrogenation reaction of 2, 3, 5-trimethylhydroquinone for synthesizing 2, 3, 5-trimethylhydroquinone has low and volatile catalyst activity, and the catalyst which has high activity and can be repeatedly used and the preparation method thereof are provided.
In order to solve the technical problems, the technical scheme is as follows:
a catalyst for the conversion of 2, 3, 5-Trimethylbenzoquinone (TMBQ) to 2, 3, 5-Trimethylhydroquinone (TMHQ), characterized by: catalyst is made of metal organic framework material NH functionalized by amino2-UiO-66(Hf) derived HfO2Amorphous carbon and noble metal Pd nanoparticles, in which HfO2The weight ratio of the noble metal Pd to the amorphous carbon is 1.4-5, and the content of the noble metal Pd is 0.5-5% of the total weight of the catalyst.
The preparation method of the catalyst comprises the following steps:
(1) hafnium tetrachloride, 2-aminoterephthalic acid and dimethylformamide were added in a molar ratio of 1: 1: 1000, putting the mixture into a conical flask to obtain a mixed solution, adding deionized water and an HCl solution into the obtained mixed solution, adjusting the pH to 3-4, and stirring for 30 min;
(2) h with a concentration of 0.055mol/L2PdCl4Slowly dripping the solution into the mixed solution obtained in the step (1), performing ultrasonic treatment for 10min, then placing an erlenmeyer flask in an oil bath, stirring for 10h at 35 ℃, then raising the temperature to 75 ℃, stirring for 15h, then raising the temperature to 130 ℃, and reducing for 4h to obtain a solid, wherein the weight of the added noble metal Pd is 0.5-5% of the total weight of the catalyst;
(3) washing the solid obtained in the step (2) with dimethylformamide and methanol in sequence, and drying the solid obtained after suction filtration at 80-150 ℃ for 6-20 h to obtain Pd @ NH2-UiO-66(Hf);
(4) Adding the solid obtained in the step (3) into N2Roasting at 500-700 ℃ for 5h at the heating rate of 5 ℃/min in the atmosphere, and cooling to room temperature to obtain black powder, namely the catalyst Pd/HfO2@C。
The application of the catalyst in converting 2, 3, 5-trimethylbenzoquinone into 2, 3, 5-trimethylhydroquinone is characterized in that: the catalyst is used for the reaction of synthesizing 2, 3, 5-trimethylhydroquinone by hydrogenating 2, 3, 5-trimethylbenzoquinone, the raw materials are 2, 3, 5-trimethylbenzoquinone and hydrogen, the 2, 3, 5-trimethylbenzoquinone, the catalyst and isopropanol are added into a polytetrafluoroethylene reaction kettle for reaction, the hydrogen pressure is controlled to be 0.5MPa, and the reaction temperature is controlled to be 40 ℃.
Considering that the incorporation of nitrogen can improve the interaction force of metal-carrier, the invention selects organic ligand 2-amino terephthalic acid containing N element and hafnium ion to construct NH2-UiO-66(Hf) is used as a sacrificial template, and N-doped HfO is obtained after subsequent inert atmosphere heat treatment2@ C material. In the design synthesis of NH2Introducing noble metal Pd ions while introducing-UiO-66 (Hf), and then preparing Pd/HfO through proper subsequent treatment2@ C composite material. Due to the introduction of C and N elements in the composite material, HfO of small-grain tetragonal phase2The stability of the composition is obviously improved. In addition, Pd is NH substituted at the same time of synthesizing MOF2The radicals effectively chelate and are then encapsulated in NH2-UiO-66(Hf) nanocage,the Pd aggregation problem is not easy to occur in the heat treatment process. Thus, the Pd particles have small size and are embedded in HfO with high dispersion2The @ C gap can effectively solve the problem of Pd loss in the use process, so that the catalyst is relative to Pd @ NH2-UiO-66(Hf) or Pd @ UiO-66(Hf), which not only has high catalytic activity and selectivity but also has excellent reusability when used for converting 2, 3, 5-trimethylbenzoquinone into 2, 3, 5-trimethylhydroquinone.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited thereto.
Example 1
Weighing 0.16g of hafnium tetrachloride and 0.093g of 2-amino terephthalic acid, dissolving in a conical flask filled with 40mL of dimethylformamide to obtain a mixed solution, dropwise adding 0.15mL of deionized water and 1mLHCl, and stirring for 10 min; 0.09mL of H with a concentration of 0.055mol/L2PdCl4Slowly dripping the solution into the mixed solution, and performing ultrasonic treatment for 10 min; then placing the conical flask in an oil bath, stirring for 10h at 35 ℃, then raising the temperature to 75 ℃, stirring for 15h, raising the temperature to 130 ℃, and reducing for 4 h; washing the obtained mixture with dimethylformamide and methanol in sequence, centrifuging, drying the sample in a vacuum drying oven at 80 ℃ for 6h, and drying in a vacuum drying oven at 150 ℃ for 6h to obtain the noble metal Pd @ NH with the weight of 0.5 percent2-UiO-66 (Hf); the solid obtained is in N2Roasting at 600 ℃ for 5h at the heating rate of 5 ℃/min in the atmosphere, and cooling to room temperature to obtain black powder, namely HfO2And amorphous carbon in a weight ratio of 2.3, noble metal in a weight ratio of 0.5% Pd/HfO2@ C catalyst.
Taking 0.5 percent Pd/HfO20.020g of @ C catalyst is applied to the reaction of synthesizing 2, 3, 5-trimethylhydroquinone by hydrogenating 2, 3, 5-trimethylbenzoquinone: 0.5g of reactant 2, 3, 5-trimethylbenzoquinone, the reaction temperature is 40 ℃, the hydrogen pressure is 0.5MPa, the reaction time is 75min, and the reaction result is as follows: the TMHQ yield is 100%.
Example 2
0.16g of hafnium tetrachloride and 0.093g of 2-aminoterephthalic acid were weighed and dissolved in a flask containing 40mL of dimethylformamide to obtain a mixed solution, and the mixed solution was added dropwise0.15mL of deionized water and 1mLHCl, and stirring for 10 min; 0.35mL of H with a concentration of 0.055mol/L2PdCl4Slowly dripping the solution into the mixed solution, and performing ultrasonic treatment for 10 min; then placing the conical flask in an oil bath, stirring for 10h at 35 ℃, then raising the temperature to 75 ℃, stirring for 15h, raising the temperature to 130 ℃, and reducing for 4 h; washing the obtained mixture with dimethylformamide and methanol in sequence, centrifuging, and drying the sample in a vacuum drying oven at 80 ℃ for 20h to obtain the noble metal Pd @ NH with the weight of 2%2-UiO-66 (Hf); the solid obtained is in N2Roasting at 500 deg.C for 5h at a temperature rise rate of 5 deg.C/min under atmosphere, and cooling to room temperature to obtain black powder, i.e. HfO2And amorphous carbon in a weight ratio of 1.4, noble metal in a weight ratio of 2% Pd/HfO2@ C catalyst.
Taking 2% Pd/HfO20.020g of @ C catalyst is applied to the reaction of synthesizing 2, 3, 5-trimethylhydroquinone by hydrogenating 2, 3, 5-trimethylbenzoquinone: 0.5g of reactant 2, 3, 5-trimethylbenzoquinone, the reaction temperature is 40 ℃, the hydrogen pressure is 0.5MPa, the reaction time is 75min, and the reaction result is as follows: the TMHQ yield was 95%.
Example 3
Weighing 0.16g of hafnium tetrachloride and 0.093g of 2-amino terephthalic acid, dissolving in a conical flask filled with 40mL of dimethylformamide to obtain a mixed solution, dropwise adding 0.15mL of deionized water and 1mLHCl, and stirring for 10 min; 0.9mL of H with a concentration of 0.055mol/L2PdCl4Slowly dripping the solution into the mixed solution, and performing ultrasonic treatment for 10 min; then placing the conical flask in an oil bath, stirring for 10h at 35 ℃, then raising the temperature to 75 ℃, stirring for 15h, raising the temperature to 130 ℃, and reducing for 4 h; washing the obtained mixture with dimethylformamide and methanol in sequence, centrifuging, and drying the sample in a vacuum drying oven at 150 ℃ for 6h to obtain Pd @ NH with the weight of the noble metal of 5%2-UiO-66 (Hf); the solid obtained is in N2Roasting at 700 ℃ for 5h at the heating rate of 5 ℃/min in the atmosphere, and cooling to room temperature to obtain black powder, namely HfO2And amorphous carbon in a weight ratio of 5, noble metal in a weight ratio of 5% Pd/HfO2@ C catalyst.
Taking 5% Pd/HfO20.020g of @ C catalyst for 2, 3, 5-trimethylbenzoquinoneHydrogenation for synthesizing 2, 3, 5-trimethylhydroquinone: 0.5g of reactant 2, 3, 5-trimethylbenzoquinone, the reaction temperature is 40 ℃, the hydrogen pressure is 0.5MPa, the reaction time is 75min, and the reaction result is as follows: the TMHQ yield was 80%.
Example 4
0.5% Pd @ HfO prepared as in example 1 was taken20.020g of @ C catalyst is used for the reaction of synthesizing 2, 3, 5-trimethylhydroquinone by hydrogenating 2, 3, 5-trimethylbenzoquinone, 0.5g of reactant 2, 3, 5-trimethylbenzoquinone is reacted at the temperature of 40 ℃ and the hydrogen pressure of 0.5MPa for 75 min. The catalyst is repeatedly used for 20 times, and the TMHQ yield is kept at 100 percent.
Comparative example 1
0.5% Pd @ NH prepared as in example 1 was taken20.020g of-UiO-66 (Hf) catalyst is used for the reaction of synthesizing 2, 3, 5-trimethylhydroquinone by hydrogenating 2, 3, 5-trimethylbenzoquinone, 0.5g of reactant 2, 3, 5-trimethylbenzoquinone is reacted at the temperature of 40 ℃ and the hydrogen pressure of 0.5MPa for 75 min. The TMHQ yield is 73%, and the activity of the catalyst is greatly reduced to 30% after the catalyst can be repeatedly used for 8 times.
Comparative example 2
Applying 0.020g of commercial 5.0% Pd/C catalyst to the reaction of synthesizing 2, 3, 5-trimethylhydroquinone by hydrogenating 2, 3, 5-trimethylbenzoquinone: 0.5g of 2, 3, 5-trimethylbenzoquinone is reacted for 75min at the temperature of 40 ℃ and the hydrogen pressure of 0.5 MPa. The TMHQ yield is 54 percent, and the activity is reduced to 25 percent after the catalyst can be repeatedly used for 2 times.
Comparative example 3
Weighing 0.16g of hafnium tetrachloride and 0.085g of terephthalic acid, dissolving in a conical flask filled with 40mL of dimethylformamide to obtain a mixed solution, dropwise adding 1mLHCl, and stirring for 10 min; 0.09mL of H with a concentration of 0.055mol/L2PdCl4Slowly dripping the solution into the mixed solution, and performing ultrasonic treatment for 10 min; then placing the conical flask in an oil bath, stirring for 10h at 35 ℃, then raising the temperature to 75 ℃, stirring for 15h, raising the temperature to 130 ℃, and reducing for 4 h; washing the obtained mixture with dimethylformamide and methanol, centrifuging, drying the sample in a vacuum drying oven at 80 deg.C for 6h, and drying in a vacuum drying oven at 150 deg.C for 6h to obtain Pd with noble metal weight of 0.5%@ UiO-66 (Hf); the solid obtained is in N2Roasting at 600 ℃ for 5h at the heating rate of 5 ℃/min in the atmosphere, and cooling to room temperature to obtain black powder, namely HfO2And amorphous carbon in a weight ratio of 2.3, noble metal in a weight ratio of 0.5% Pd-HfO2@ C catalyst.
Taking 0.5 percent Pd-HfO20.020g of @ C catalyst is applied to the reaction of synthesizing 2, 3, 5-trimethylhydroquinone by hydrogenating 2, 3, 5-trimethylbenzoquinone: 0.5g of reactant 2, 3, 5-trimethylbenzoquinone, the reaction temperature is 40 ℃, the hydrogen pressure is 0.5MPa, the reaction time is 75min, and the reaction result is as follows: the TMHQ yield was 36%.
Claims (4)
1. A catalyst for the conversion of 2, 3, 5-Trimethylbenzoquinone (TMBQ) to 2, 3, 5-Trimethylhydroquinone (TMHQ), characterized by: the catalyst is made of metal organic framework material NH functionalized by amino2-UiO-66(Hf) derived HfO2Amorphous carbon and noble metal Pd nanoparticles, wherein HfO2The weight ratio of the noble metal Pd to the amorphous carbon is 1.4-5, and the content of the noble metal Pd is 0.5-5% of the total weight of the catalyst.
2. The method for preparing the catalyst according to claim 1, comprising the steps of:
(1) hafnium tetrachloride, 2-aminoterephthalic acid and dimethylformamide were added in a molar ratio of 1: 1: 1000, putting the mixture into a conical flask to obtain a mixed solution, adding deionized water and an HCl solution into the obtained mixed solution, adjusting the pH to 3-4, and stirring for 30 min;
(2) h with a concentration of 0.055mol/L2PdCl4Slowly dripping the solution into the mixed solution obtained in the step (1), performing ultrasonic treatment for 10min, then placing an erlenmeyer flask in an oil bath, stirring for 10h at 35 ℃, then raising the temperature to 75 ℃, stirring for 15h, then raising the temperature to 130 ℃, and reducing for 4h to obtain a solid, wherein the weight of the added noble metal Pd is 0.5-5% of the total weight of the catalyst;
(3) washing the solid obtained in the step (2) with dimethylformamide and methanol in sequence, and drying the solid obtained after suction filtration at 80-150 ℃ for 6-20 h to obtain Pd @ NH2-UiO-66(Hf);
(4) Adding the solid obtained in the step (3) into N2Roasting at 500-700 ℃ for 5h at the heating rate of 5 ℃/min in the atmosphere, and cooling to room temperature to obtain black powder, namely the catalyst Pd/HfO2@C。
3. Use of a catalyst according to claim 1 for the conversion of 2, 3, 5-trimethylbenzoquinone to 2, 3, 5-trimethylhydroquinone.
4. Use according to claim 3, characterized in that: the catalyst is used for the reaction of synthesizing 2, 3, 5-trimethylhydroquinone by hydrogenating 2, 3, 5-trimethylbenzoquinone, the raw materials are 2, 3, 5-trimethylbenzoquinone and hydrogen, the 2, 3, 5-trimethylbenzoquinone, the catalyst and isopropanol are added into a polytetrafluoroethylene reaction kettle for reaction, the hydrogen pressure is controlled to be 0.5MPa, and the reaction temperature is controlled to be 40 ℃.
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CN106117017A (en) * | 2016-06-21 | 2016-11-16 | 南通柏盛化工有限公司 | The method of bionic catalysis reduction preparation 2,3,5 trimethylhydroquinone |
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CN106117017A (en) * | 2016-06-21 | 2016-11-16 | 南通柏盛化工有限公司 | The method of bionic catalysis reduction preparation 2,3,5 trimethylhydroquinone |
Non-Patent Citations (1)
Title |
---|
"Pd nanoparticles encaged within amine-functionalized metal-organic frameworks: Catalytic activity and reaction mechanism in the hydrogenation of 2,3,5-trimethylbenzoquinone";Shuang Zheng et al.;《Chemical Engineering Journal》;20170716;全文 * |
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